Vat dyestuffs



Patented Oct. 3, 1939 This invention relates vat-dyestuffs by the 7 2,175,122 ENT OFFICE 2,175,122 VAT DYESTUFFS Walter Kern, Sissach, Switzerland,

assignor to the firm of Society of Chemical Industry in Basle,

Basel, Switzerland N0 Drawing.

Application January 9, 1932, Se-

3 Claims. (01. 260-365) to the manufacture of action of an ortho-dicarboxylic acid-anhydride on fluoranthene in presence of a condensing agent, wherein for 1 mol of 5 fluoranthene at least 2 mols of the ortho-dicarboxylic acid-anhydride are used.

As ortho-dicarboxylic acid-anhydrides may be used, for example, phthalic-anhydride, naphthalene-2 B-dicarboxylic acid-anhydride, anthraquinone-dicarboxylic acid-anhydride and substitution products of these anhydrides, for instance halogenor alkylanhydrides.

Suitable condensing aluminium halides, such or ferric chloride; these be used in presence" of ortho-dicarboxylic acidagents are, for instance,

as aluminium chloride, condensing agents may an additional substance which lowers the melting point, for instance an alkali halide (sodium ride, or both) or of a chloride or potassium chlosolvent or a dispersing agent for example benzene, trichlorobenzene, chloronaphthalene or nitrobenzene.

The process may consist in condensing 1 mol fluoranthene with at least 2 boxylic acid-anhydride a single stage, preferabl producing in one stage mols ortho-dicarto the vat-dyestuff in y at 120160 C., or in from 1 mol fluoranthene and 1 mol ortho-dicarboxylic acid-anhydri-de a mono-ketone-carboxylic mg di'kewne which then in a Second Stage may are also obtained when exchanging the phthalic acid or a correspondbe converted into the vat-dyestuff by condensation with at least 1 /2 mols ortho-dicarboxylic acid-anhydride, preferably at 120-160 C.

A further feature of the invention consists in the treatment of the products obtained in the manner described above with a substituting agent or a condensing agent or both,

furic acid, an aldehyde,

for instance sulfor example formaldehyde, or a halogenating agent, for example chlorine 0r bromine, whereby further valuable products are obtained.

The new products may be purified by one or more crystallizations fr boiling point, preferably conversion into their salts an oxidizing agent, for inof alkali hypochlorite; they by treatment with stance a solution om a solvent of high trichlorobenzene, or by from strong acids, or

may be converted by known methods into leucoderivatives, for example esters.

The products of this the leuco-sulfuric acid invention are in part very fast.

The following examples illustrate the invention, the parts being by Weight, unless otherwise stated, and the parts by weight and parts by volume being related as i s the kilo to the liter:-

Example 1 20.2 parts of fluoranthene, 90 parts of phthalic anhydride and 180 parts of aluminium chloride are intimately mixed together and the mixture is baked for 6 hours'at a temperature of 85-90 C. For completing the reaction the temperature is raised in stages, namely 6 hours at 110120 C. and 8 hours at 128-130 C. After cooling, the mass is comminuted and introduced for separating the aluminium chloride into dilute h drochloric acid which is boiled; the mass is then filtered and the residueextracted first with water and then with dilute sodium carbonate solution. After recrystallization from trichlorobenzene the 'dyestuff' of the formula this example for the equivalent chloro-phthalic anhydride.

anhydride used in quantity of bromoor Example 2 315 parts of aluminium chloride, 66 parts of potassium chloride and 45 parts of common salt are together melted at 11211'l 'C., and then there is introduced into the melt, in portions and in the course of half-an-hour, a mixture of 20.2 parts of fluoranthene and 60 parts of phthalic anhydride. For completing the reaction the mass is stirred for 6 hours at 130-135 C. The cooled mass is comminuted, introduced into dilute hydrochloric acid, which is then boiled. After filtering, the solid matter is extracted with boiling water. For purification this crude dyestuff is extracted with dilute sodium carbonate solution and then with alcohol. The dyestuif is a dark brown powder, which may be purified by recrystallization from trichlorobenzene. It dissolves in concentrated sulfuric acid to a cherry red solution and dyes cotton in a blue vat yellow tints of very good fastness.

Erample 3 and the mixture is heated for 24 hours at 140-145 C. The cooled mass is comminuted and introduced into dilute hydrochloric acid for separating the aluminium chloride. After boiling this mixture it is filtered and the solid mat-' Example 4 2.3 parts of the dyestuff obtained as described in Example 1 are suspended in parts of nitrobenzene, some iodine is added and, at 20 0., in the course of half-an-hour, 3 parts of sulfuryl chloride are added by drops. In order to hasten the reaction the temperature is raised to 62-66 C. and kept there for 16 hours. After cooling and filtering, the solid matter is washed with benzene and alcohol and dried. This chlorinated dyestuff is a yellow powder, soluble in concentrated sulfuric acid to a cherry red solution and dyeing cotton in a blue vat very fast yellow tints.

Example 5 2.3 parts of the dyestuif made as described in Example 1 are suspended in 60 parts of nitrobenzene, a little iodine is added and in the course of half-an-hour, at 20 0., 3.4 parts of bromine are added by drops. The temperature is now raised to -85 C. and kept there for 16 hours while stirring. After cooling, the whole is filtered and the solid matter washed with benzene and alcohol and dried. This brominated dyestufi is a brown-orange powder, soluble in concentrated sulfuric acid to a cherry red solution and dyeing cotton in a blue vat yellow-brown tints of very good fastness.

What I claim is:

1. Vat dyestuffs of the general formula wherein the two Rs represent aryl radicals selected from the group consisting of the benzene and naphthalene series and R1 represents a fluoranthene radical in which two adjacent carbon atoms together form a siX-membered carbon ring with each grouping.

2. Vat dyestuffs of the general formula t 4% wherein the two Rs represent and R1 represents a fiuoranthene radical in wherein the two and two adJacent grouping. 

